WO1998045341A1 - Self-light-stabilized photochromic polymer, its preparation and articles containing same - Google Patents
Self-light-stabilized photochromic polymer, its preparation and articles containing same Download PDFInfo
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- WO1998045341A1 WO1998045341A1 PCT/US1998/006248 US9806248W WO9845341A1 WO 1998045341 A1 WO1998045341 A1 WO 1998045341A1 US 9806248 W US9806248 W US 9806248W WO 9845341 A1 WO9845341 A1 WO 9845341A1
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- 0 *C(c1ccccc1)=C Chemical compound *C(c1ccccc1)=C 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
- C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Definitions
- Self-light-stabilized photochromic polymer its preparation and articles containing same
- photochromic polymers proposed notably for ophthalmic applications, whose polymer matrix includes at least one photochromic coloring agent.
- Said photochromic coloring agents generally consist of spiropyrans, spiroxazines or chromenes. They may intervene in combination.
- HALS Hindered Amine Light Stabilizers
- HALS sterically hindered amines
- an asymmetric diaryloxalamide in formulations containing a spiroxaz- ine(s)/chromene(s) combination
- These amines proposed as photostabilizers for photochromic polymers, are generally of a heterocycle-based complex chemical structure and most of them intervene free, dispersed within the matrix of said polymers.
- the Applicant presently proposes an original solution to this technical problem of the photostabilization of said photochromic polymers.
- the Applicant in fact proposes the original intervention of original stabilizers.
- Said stabilizers are monomers or oligomers which are active via non-cyclic tertiary amine groups and they intervene chemically bound to the polymer matrix. They are added prior to the development of said polymer matrix by radical polymerization and they intervene, as co-monomer or co-oligomer, in said radical polymerization. They are known chemical compounds proposed for an original use as photochromic polymer photostabilizers.
- Said photochromic polymers which incorporate them in their structure, in their carbon skeleton, constitute the first object of the present invention.
- the first object of the present invention is photochromic polymers which carry non-cyclic tertiary amine-functionalized pendant groups.
- Said polymers are photochromic insofar as their matrix includes at least one photochromic coloring agent.
- Said thermoplastic or thermoreticulated polymers are self-stabilized insofar as the stabilizers that they contain are chemically bound to their matrix, insofar as said stabilizers constitute a part of their matrix. Furthermore, said stabilizers are thus homogeneously distributed.
- non-cyclic tertiary amine-functionalized pendant groups are of the [di(substituted)amino][(C2-C3)alkyl]carboxy type:
- the photochromic polymers of the invention are thermoplastic ones or thermoreticulated ones. It is possible for the large majority of them to be obtained by radical co-polymerization of a composition including acrylic and/or methacrylic and/or alkenyl, notably vinylic or allylic, monomers and/or oligomers. Such compositions are described in more detail further on in the present text. Characteristically, in order to generate the polymers of the invention, said compositions contain an effective amount of at least one monomer and/or oligomer having a non-cyclic tertiary amine function in its formula.
- compositions contain an effective amount of a monomer of the following formula:
- - n is 2 or 3; - R 2 and R 3 , identical or different, represent independently a methyl or ethyl group; and are advantageously identical.
- Said monomer is particularly preferably of the following formula:
- the monomers and/or oligomers which intervene characteristically in the context of the present invention have in their formula, on the one hand, a non-cyclic tertiary amine function (photostabilizing function), and on the other hand, a function which is reactive in the sense of the radical polymerization which generates the stabilized photochromic polymer.
- Said reactive function is generally of the acrylic, methacrylic or alkenyl type, notably vinylic or allylic.
- the reactive function co-polymerizes with the reactive functions of the various constituents of the polymer matrix, reactive functions which are generally of the same type (vide supra).
- said monomers and/or oligomers (having at least one non-cyclic tertiary amine function in their structure) intervene in an effective amount.
- This amount is generally between 0.05 and 5% by weight, and advantageously between 0.2 and 0.6% by weight of the weight of the composition to be polymerized.
- Said preferred polymers are obtained by radical co- polymerization of a composition containing: (a) at least one monomer of formula (I):
- R ⁇ H or CH3 ; said monovinyl monomer advantageously consisting of styrene ; (c) an effective amount of at least one photochromic coloring agent conferring photochromic properties to said polymer; said coloring agent being selected from the group consisting of spiroxazines, spiropyrans and chromenes, and advantageously consisting of at least one spiroxazine, of at least one chromene, or a mixture of spiroxazine(s)/chromene(s); (d) an effective amount of at least one monomer and/or oligomer having at least one non-cyclic tertiary amine function in its formula; said monomer advantageously being of the formula below:
- - R is hydrogen or a methyl group
- composition generally further contains an effective amount of at least one chain transfer agent and an effective amount of at least one radical polymerization initiator.
- the composition may also further contain: (e) at least one aromatic divinyl monomer of formula (III) :
- said divinyl monomer advantageously consisting of divinylbenzene, and/or
- R H or CH3 and R' is a straight-chain or branched alkyl radical having from 4 to 16 carbon atoms, an optionally substituted (generally by a C,-C 6 alkyl group) methylphenyl or methylphenoxy radical or polyoxyethoxylated group of formula:
- the intervening compounds, or compounds which can intervene in the composition of the preferred polymer of the invention shall now be examined in greater detail.
- the monomers (a) of formula (I) are well-known and are commercially available. It is noted that it is a matter of first monomers of formula (A) in the sense of the WO-A-92/05209 document.
- Said monomer is notably marketed by AKZO NOBEL (NL), under the commercial designation DIACRYL 121.
- the monomers of formula (I) generally intervene in the composition to be polymerized at a rate of 50 to 90 % by weight. If they intervene in too low an amount, the polymerizable composition (or matrix) tends to shrink during its polymerization, inducing a premature turning-out of the mold which is itself responsible for a deterioration of the optical properties of the final material. If they intervene in too great an amount, it is also observed that the final material has mediocre optical properties.
- the aromatic monovinyl monomers (b) of formula (II) (styrene and/or methylstyrene) intervene in combination with the monomers of formula (I) in order to loosen the polymer network.
- Said styrene constitutes the particularly preferred compound of this class of monomers.
- Said monomers of formula (II) generally intervene in the composition to be polymerized at the rate of 5 to 40% by weight, advantageously at the rate of 8 to 30% by weight. If they intervene in too low an amount, no expected effect of the tensions within the matrix are observed (birefringence phenomena are observed...); a matrix is also obtained which has a low refractive index. If they intervene in too great an amount, it is observed that the matrix tends to stick to the mold during the polymerization and a decrease in the photochromic properties (above all kinetically) is also observed.
- the preferred polymers of the invention insofar as it is a matter of (stabilized) photochromic materials, further contain an effective amount of at least one photochromic coloring agent (c) in their matrix.
- Said coloring agent is selected from spiropyrans, spiroxazines and chromenes (or a combination thereof) which are endowed with photochromic properties. Very many photochromic coloring agents of this type are described in the literature and are available commercially. .
- Spiroxazine coloring agents which may be used in the context of the present invention, have notably been described in the following patents: US-A-3,562,172, 4,634,767, 4,637,968, 4,720,547, 4,756,973, 4,785,097, 4,792,224, 4,816,584, 4,831,142, 4,909,963, 4,931,219, 4,936,995, 4,986,934, 5,114,621, 5,139,707, 5,233,038, 4,215,010, 4,342,668, 4,699,473, 4,851,530, 4,913,544, 5,171,636, 5,180,524, 5,166,345, in the applications EP-A- 0 508 219, 0 232 295 and 0 171 909 and in the application FR-A-2 738 248 (of the Applicant).
- Chromene coloring agents which may be used within the context of the present invention are notably described in the patents US-A-3,567,605, 4,889,413,
- Said chromenes may notably consist of naphthopyrans.
- compositions of the invention contain an effective amount of at least one photochromic coloring agent. It is in fact frequent, within the context of the present invention, to bring about a combination of photochromic coloring agents with the aim of obtaining at the darkened state a specific tint, notably gray or brown.
- the intervening photochromic filler comprises a spiroxazine(s)/chromene(s) combination. Such a composition may notably contain two spiroxazines and two chromenes.
- Said photochromic coloring agents may themselves very well contain a polymerizable and/or cross-linkable reactive group in their chemical formula. They themselves then intervene (just as the stabilizers which are « associated » to them), as co-monomers in the composition to be polymerized, and are chemically bound, grafted to the matrix of said polymerized composition.
- the polymers of the invention notably those obtained from monomers (a) and (b) specified above, contain their photochromic coloring agent(s), free or bound to their matrix.
- the composition of the preferred polymers of the invention is now reverted to.
- the composition contains an effective amount of at least one monomer and/or oligomer having at least one non-cyclic tertiary amine function in its formula (said function being advantageously of the [di(substituted)amino][(C2-C3)alkyl]carboxy type and particularly preferably of the [di(C ⁇ -C2)alkylamino][linear(C2-C3)alkyl]carboxy type); said monomer advantageously having the following formula :
- - Rj is hydrogen or a methyl group
- - n is 2 or 3; - R 2 and R 3 are identical or different and represent independently a methyl or ethyl group; and are advantageously identical.
- This monomer and/or oligomer which has at least one non-cyclic tertiary amine function in its formula is advantageously such as specified above. It is advantageously DEAEMA. It intervenes advantageously in the amounts indicated: 0.05 to 5% by weight, preferably 0.2 to 0.6% by weight.
- Said compound of formula (III) consists of divinylbenzene (DVB) or di(methylvinyl)benzene.
- Divinylbenzene (DVB) is the particularly preferred compound of formula (III).
- the intervention of at least one compound of formula (III) is advantageous notably in that said compound moderates, in a general manner, the effects of the compound of formula (II).
- the beneficial action of such a compound of formula (III) on the expression of the photochromic properties has notably been demonstrated.
- Said polymerizable composition advantageously contains a plasticizer. Its photochromic properties may be improved by bringing such a plasticizer in.
- the Applicant has in fact shown in a surprising way that the incorporation of plasticizers (in reasonable amounts) in polymerizable compositions based on monomers of formula (I) and (II) filled with photochromic coloring agent(s), has beneficial effects on the photochromic properties of said compositions without altering their mechanical properties.
- Said plasticizer may notably consist of triphenylphosphate or a phthalate.
- the composition from which the polymer of the invention is developed comprises at least one phthalate.
- Said phthalate is in principle selected from the saturated phthalates, advantageously sterically hindered, and unsaturated phthalates having one or two substituents.
- saturated phthalates at least one saturated phthalate
- they are not chemically bound to the polymer matrix insofar as they are not monomers. They are dispersed in said matrix. It is therefore understood that, for problems of stability, it is recommended that sterically hindered phthalates are brought in.
- saturated phthalates which include two substituents, which intervene advantageously as plasticizer in the polymerizable compositions from which polymers of the invention are obtained.
- Said phthalates are grouped into three groups.
- Linear phthalates dialkylphthalates, whose alkyl groups, identical or different, generally have from 1 to 12 carbon atoms (and may also have a larger number of carbon) ; and notably : dimethylphthalate - diethylphthalate -dibutylphthalate - dihexylphthalate - diheptylphthalate - dioctyl(tere)phthalate - dinonylphthalate - diundecylphthalate - ditridecylphthalate - butyloctylphthalate - undecyl dodecylphthalate.
- Hindered phthalates dialkylphthalates, of the same type as those indicated above, of which at least one of the alkyl groups is branched; and notably: diisobutylphthalate - diisoheptylphthalate - diisooctylphthalate - diisononyl- phthalate - diisodecylphthalate - di(2-ethylhexyl)phthalate - di (1-methylheptyl)- phthalate or dialkylcycloalkylphthalates - dicycloalkylphthalates dialkylphenylalkylphthalates and diphenylalkylphthalates (whose alkyl groups, as indicated above, generally have from 1 to 12 carbon atoms); and notably: cyclohexyl isooctylphthalate - dicyclohexylphthalate - butylcyclohexylphthalate - butylbenzylphthalate.
- phthalates and notably phthalates substituted with alkoxy groups, whose alkyl groups generally have from 1 to 12 carbon atoms, such as: dimethoxyethylphthalate - dibutoxyethylphthalate - dibutoxyethoxyethylphthalate.
- alkoxy groups whose alkyl groups generally have from 1 to 12 carbon atoms
- dimethoxyethylphthalate - dibutoxyethylphthalate - dibutoxyethoxyethylphthalate As saturated phthalate, it is most particularly preferred to bring in butylphthalate (DBP) and/or dioctylphthalate (DOP), notably in the form of dioctylterephthalate.
- DBP butylphthalate
- DOP dioctylphthalate
- unsaturated phthalates at least one unsaturated phthalate
- they are chemically bound to the polymer matrix insofar as their double bond(s) has (have) intervened during the radical polymerization. They have in fact intervened as a monomer. They are found thus perfectly anchored and stabilized in the polymer matrix. It is most particularly recommended to bring in diallylphthalate as an unsaturated phthalate.
- the plasticizers which intervene advantageously in the polymerizable composition from which the preferred polymers of the invention are obtained generally intervene at a rate of 1 to 10% by weight. If they intervene in too low an amount their beneficial action on photochromic properties do not manifest themselves. If they intervene in too high an amount, their influence becomes harmful to the mechanical properties.
- the polymerizable composition also advantageously contains at least one compound (monomer) of formula (IV). It is a matter of (meth)acrylic monomers such as described above. It may notably be a matter of butyl, pentyl, hexyl, heptyl, octyl or 2-ethylhexyl(meth)acrylate or even ethyltriglycol- (meth)acrylate. 2-Ethylhexylmethacrylate (EHMA) is the preferred compound of formula (IV).
- EHMA 2-Ethylhexylmethacrylate
- the presence of this type of compound proves notably to be advantageous for the turning-out of the polymerized material and for carrying out the finishing treatments of the latter.
- the intervention of this type of monomer whose presence has the disadvantage of lowering the refractive index, is generally limited to 20% by weight.
- the expected beneficial effect generally manifests itself from the intervention of a few percent by weight. It is therefore generally recommend to bring in this type of compound at a rate of 4 to 15% by weight.
- the intervention of the compounds of formula (III) and/or (IV) and/or plasticizer(s) is not essential. It proves nevertheless to be advantageous.
- a certain synergic effect has been demonstrated, on the photochromic properties of the plasticizer and of the compound of formula (III).
- the compounds of formula (I), (II), (III), (IV) and the plasticizer(s) are the principal constituents (insofar as they intervene or are able to intervene in relatively consistent amounts) of the compositions from which the polymers of the invention are generated.
- Said polymers are obtained from said compounds (monomers) by a classical radical co-polymerization per se.
- Said radical co-polymerization is generally carried out as specified above in the presence of an effective amount of at least one chain transfer agent and of at least one radical polymerization initiator.
- the radical co-polymerization is characteristically carried out in the presence of at least one monomer and/or oligomer which has at least one non-cyclic tertiary amine function in its formula.
- the chain transfer agent generally intervenes at a maximal content of 5% by weight, advantageously at a rate of 0.01 to 2% by weight, compared to the weight of the monomers to be co-polymerized. It is noted here that it is possible to do away with the presence of such a chain transfer agent in the hypothesis where the material is prepared under a reduced thickness (e ⁇ 2.0 mm). In this hypothesis, problems of release of heat are not met... In order to prepare a material of the invention having a thickness of greater than 2.0 mm, the presence of a chain transfer agent in the amounts indicated above is almost essential. It is highly inadvisable to go over the maximal content of 5% indicated above since then the glass transition temperature of the material prepared becomes much too low.
- linear alkane thiols generally have from 2 to 18 carbon atoms, advantageously from 4 to 16 carbon atoms.
- linear alkane thiols are butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, decanethiol, dodecanethiol and tetradecanethiol.
- chain transfer agents such as alkane thiols (of the above type) substituted with at least one aryl or alkyl radical or thiophenols.
- the intervening radical polymerization initiator or catalyst must itself as well be « inert » towards photochromic coloring agent(s) present. It is for this reason that the Applicant recommends not using initiators of the peroxide type.
- the Applicant recommends the use of radical polymerization initiator(s) selected from the diazo compounds. These compounds are familiar to the person skilled in the art and are commercially available. Examples of such diazo compounds are azobisisobutyronitrile (AIBN) and 2,2'-azobis(2-methylbutyronitrile) (AMBN), the latter being preferred.
- the catalyst is generally used at a rate of 0.01 to 1% by weight, preferably at a rate of 0.05 to 0.5% by weight, with respect to the weight of the monomers present.
- the materials of the invention are photochromic transparent organic materials. It is not excluded from the context of the present invention to bring into said composition to be polymerized, as has been already indicated, an effective amount of at least one non-photochromic coloring agent so that the material resulting from the polymerization has a fixed base tint.
- the claimed polymers can be obtained by radical polymerization of a composition principally containing about: 50 to 90 % by weight of at least one monomer (a) of formula (I) ; 5 to 40 % by weight of at least one monomer (b) of formula (II) ; 0.05 to 5 % by weight of at least one monomer and/or oligomer (d) having at least one non-cyclic tertiary amine function in its formula; 0 to 10 % by weight of at least one plasticizer ;
- Said composition obviously contains as well an effective amount of at least one photochromic coloring agent.
- the first object of the presently claimed invention self-light-stabilized photochromic polymers insofar as their structure integrates non-cyclic tertiary amine functionalized pendant groups.
- the invention relates to photochromic articles constituted wholly or in part of a polymer of the invention.
- Non-limiting examples of such articles are ophthalmic corrective lenses, solar lenses (the material contains a non-photochromic coloring agent), glazings for vehicles and buildings ...
- the photochromic material of the invention may constitute all the thickness of the article (mass article) or may constitute only a stratified film or layer applied onto a support.
- Ophthalmic lenses are the preferred articles and may be conveniently produced by carrying out the co-polymerization for example such as described in the US patents US-A-2,242,386, 3,136,000 or 3,881,683.
- the invention relates to the preparation of a self-light-stabilized photochromic thermoplastic or thermo- reticulated polymer comprising the radical co-polymerization of a composition containing an effective amount, as photostabilizer, of at least one monomer and/or oligomer having at least one non-cyclic tertiary amine function in its formula (said function being advantageously of the [di(substituted)amino][(C2- C3)alkyl]carboxy type and, particularly preferred, of the [di(C ⁇ - C2)alkylamino][linear(C2-C3)alkyl]carboxy) type; said monomer advantageously being of the following formula: CH
- - Ri is hydrogen or a methyl group
- - n 2 or 3 ;
- R2 and R3 are identical or different and represent independently a methyl or ethyl group; and are advantageously identical.
- the present invention relates to a particular use of monomers and/or oligomers having at least one non-cyclic tertiary amine function in its formula as well as a polymerization-reactive function.
- the polymerization used within the context of the present invention brings in, generally, several types of monomers and/or oligomers. In a particular manner, within the context of the preferred variant described in detail above, it can bring in the following types of monomers (reagents):
- composition to be polymerized may further contain, as is indicated above, various additives and notably a non-photochromic coloring agent.
- various additives and notably a non-photochromic coloring agent are illustrated by Examples 1,2, 3 and 4 hereinafter.
- Examples IT, 2T, 3T and 4T are given as comparisons. They relate to control compositions which do not include a photostabilizer in their composition.
- Test-tubes of 2 mm thickness have in fact been prepared that have been tested in order to evaluate their photochromic properties.
- Said test-tubes have been obtained by carrying out the polymerization of the polymerizable composition in an adequate mold under the following conditions: said polymerizable composition is heated gently until the start of a thermal degradation of the catalyst (radical polymerization initiator), degradation which generates free radicals. Once the temperature of 53°C is reached, it is maintained for 16 hours. After 16 hours, in the space of 3 hours, the temperature is brought to 90°C. This temperature of 90°C is then maintained for 2 hours. After this thermal treatment, the test-tubes of the material to be tested are obtained by turning-out.
- the catalyst radiation polymerization initiator
- thermal treatment specified above is that carried out by the Applicant for obtaining ophthalmological lenses from polymerizable compositions of the invention, treated in the lens molds.
- the starting materials used in the Examples are the following: Monomers
- Photochromic coloring agents Chemical type Designation Spiroxazine SPO1* Spiroxazine SPO2** Spiroxazine SPO3***
- test-tubes of the material according to the invention (Examples 1,2,3, and 4) as well as those of material which do not contain any photostabilizer (Examples IT, 2T, 3T and 4T) were prepared by polymerizing, under the above conditions, polymerizable compositions whose formulations are specified in the following Table 1.
- the photochromic properties of the materials obtained were evaluated by the slope of the measurement of one or two parameters:
- the dark state is obtained by exposing the sample under a xenon lamp (40,000 lux) for 15 minutes.
- the fatigued state of the sample is obtained by submitting said sample to the conditions of the Suntest, which consists of exposing said sample under a xenon lamp (50,000 lux) for 250 hours.
Abstract
Description
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69810759T DE69810759D1 (en) | 1997-04-04 | 1998-03-30 | SELF-LIGHT-STABILIZED PHOTOCHROMIC POLYMER, ITS PRODUCTION AND ITEMS CONTAINING THE SAME |
US09/402,598 US6316569B1 (en) | 1997-04-04 | 1998-03-30 | Self-light-stabilized photochromic polymer, its preparation and articles containing same |
EP98913293A EP0973811B1 (en) | 1997-04-04 | 1998-03-30 | Self-light-stabilized photochromic polymer, its preparation and articles containing same |
JP54284298A JP2001518960A (en) | 1997-04-04 | 1998-03-30 | Self-light-stabilized photochromic polymer, process for preparing the same, and articles containing the same |
CA002285602A CA2285602A1 (en) | 1997-04-04 | 1998-03-30 | Self-light-stabilized photochromic polymer, its preparation and articles containing same |
AU67882/98A AU6788298A (en) | 1997-04-04 | 1998-03-30 | Self-light-stabilized photochromic polymer, its preparation and articles containing same |
BR9808633-2A BR9808633A (en) | 1997-04-04 | 1998-03-30 | Photochromic polymer self-stabilized under light, its preparation and articles containing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9704128A FR2761694B1 (en) | 1997-04-04 | 1997-04-04 | PHOTOCHROMIC POLYMER, INTRINSICALLY STABLE TO LIGHT ITS PREPARATION AND ITEMS CONTAINING IT |
FR97/04128 | 1997-04-04 |
Publications (1)
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WO1998045341A1 true WO1998045341A1 (en) | 1998-10-15 |
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PCT/US1998/006248 WO1998045341A1 (en) | 1997-04-04 | 1998-03-30 | Self-light-stabilized photochromic polymer, its preparation and articles containing same |
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Country | Link |
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EP (1) | EP0973811B1 (en) |
JP (1) | JP2001518960A (en) |
CN (1) | CN1249763A (en) |
AR (1) | AR012334A1 (en) |
AU (1) | AU6788298A (en) |
BR (1) | BR9808633A (en) |
CA (1) | CA2285602A1 (en) |
DE (1) | DE69810759D1 (en) |
FR (1) | FR2761694B1 (en) |
TW (1) | TW493107B (en) |
WO (1) | WO1998045341A1 (en) |
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WO2001030866A1 (en) * | 1999-10-22 | 2001-05-03 | Wesley Jessen Corporation | Sterile photochromic hydrophilic contact lenses |
EP1598408A1 (en) * | 2004-05-19 | 2005-11-23 | Gyongtae Kim | A polymer for a photochromic compound matrix, and a matrix comprising the said polymer |
CN112571893A (en) * | 2020-11-30 | 2021-03-30 | 上海甘田光学材料有限公司 | Photochromic glass and preparation method thereof |
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WO2018124063A1 (en) * | 2016-12-28 | 2018-07-05 | 伊藤光学工業株式会社 | Optical element and production method therefor |
WO2018123077A1 (en) * | 2016-12-28 | 2018-07-05 | 伊藤光学工業株式会社 | Optical element |
CN111234623A (en) * | 2019-12-02 | 2020-06-05 | 安徽科创美涂料科技股份有限公司 | Preparation and application of photochromic real stone paint coating |
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US5266447A (en) * | 1990-07-04 | 1993-11-30 | Lintec Corporation | Photochromic composition |
US5391327A (en) * | 1992-09-25 | 1995-02-21 | Transitions Optical, Inc. | Photochromic compositions of improved fatigue resistance |
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US3322542A (en) * | 1963-11-14 | 1967-05-30 | American Cyanamid Co | Stabilization additives for photochromic compounds |
US3914510A (en) * | 1972-06-16 | 1975-10-21 | Ncr Co | Thermal sensitive transparency |
US4440672A (en) * | 1982-03-22 | 1984-04-03 | American Optical Corporation | Photochromic composition resistant to fatigue |
US4994208A (en) * | 1989-04-18 | 1991-02-19 | Ppg Industries, Inc. | Photochromic polymeric article |
-
1997
- 1997-04-04 FR FR9704128A patent/FR2761694B1/en not_active Expired - Fee Related
-
1998
- 1998-03-30 BR BR9808633-2A patent/BR9808633A/en unknown
- 1998-03-30 CN CN98803126A patent/CN1249763A/en active Pending
- 1998-03-30 JP JP54284298A patent/JP2001518960A/en active Pending
- 1998-03-30 DE DE69810759T patent/DE69810759D1/en not_active Expired - Lifetime
- 1998-03-30 WO PCT/US1998/006248 patent/WO1998045341A1/en active IP Right Grant
- 1998-03-30 AU AU67882/98A patent/AU6788298A/en not_active Abandoned
- 1998-03-30 EP EP98913293A patent/EP0973811B1/en not_active Expired - Lifetime
- 1998-03-30 CA CA002285602A patent/CA2285602A1/en not_active Abandoned
- 1998-04-03 AR ARP980101546A patent/AR012334A1/en unknown
- 1998-08-06 TW TW087113087A patent/TW493107B/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5110881A (en) * | 1989-04-18 | 1992-05-05 | Ppg Industries, Inc. | Polymerizable organic resin composition |
US5266447A (en) * | 1990-07-04 | 1993-11-30 | Lintec Corporation | Photochromic composition |
US5391327A (en) * | 1992-09-25 | 1995-02-21 | Transitions Optical, Inc. | Photochromic compositions of improved fatigue resistance |
Non-Patent Citations (1)
Title |
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See also references of EP0973811A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001030866A1 (en) * | 1999-10-22 | 2001-05-03 | Wesley Jessen Corporation | Sterile photochromic hydrophilic contact lenses |
EP1598408A1 (en) * | 2004-05-19 | 2005-11-23 | Gyongtae Kim | A polymer for a photochromic compound matrix, and a matrix comprising the said polymer |
CN112571893A (en) * | 2020-11-30 | 2021-03-30 | 上海甘田光学材料有限公司 | Photochromic glass and preparation method thereof |
CN112571893B (en) * | 2020-11-30 | 2022-06-03 | 上海甘田光学材料有限公司 | Photochromic glass and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN1249763A (en) | 2000-04-05 |
DE69810759D1 (en) | 2003-02-20 |
JP2001518960A (en) | 2001-10-16 |
EP0973811A1 (en) | 2000-01-26 |
FR2761694B1 (en) | 1999-06-25 |
AR012334A1 (en) | 2000-10-18 |
CA2285602A1 (en) | 1998-10-15 |
TW493107B (en) | 2002-07-01 |
EP0973811B1 (en) | 2003-01-15 |
EP0973811A4 (en) | 2000-07-12 |
BR9808633A (en) | 2000-05-16 |
FR2761694A1 (en) | 1998-10-09 |
AU6788298A (en) | 1998-10-30 |
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